CN1028108C - Catalyst Compsns. - Google Patents

Catalyst Compsns. Download PDF

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Publication number
CN1028108C
CN1028108C CN90100394A CN90100394A CN1028108C CN 1028108 C CN1028108 C CN 1028108C CN 90100394 A CN90100394 A CN 90100394A CN 90100394 A CN90100394 A CN 90100394A CN 1028108 C CN1028108 C CN 1028108C
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palladium
bidentate ligand
complex compound
alkyl
catalyst composition
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CN90100394A
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CN1044469A (en
Inventor
皮特拉斯·威尔海尔莫斯·尼克拉斯·玛丽亚
考尼利斯·弗兰西斯科斯·罗比克
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Shell Internationale Research Maatschappij BV
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
    • C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyethers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

Catalyst compositions suitable for the preparation of polymers of carbon monoxide and one or more olefinically unsaturated compounds, are based upon a complex of a hydrocarbyl palladium halide and a phosphorus bidentate ligand.

Description

Catalyst Compsns.
The present invention relates to the catalyst composition based on a kind of complex compound that is formed by palladium compound and phosphorous bidentate ligand, this composition is suitable to the catalyzer for preparing polymkeric substance from carbon monoxide and one or more alefinically unsaturated compounds.
Known in simple linear polymer by carbon monoxide and the preparation of one or more alefinically unsaturated compounds, the link units that derives from by carbon monoxide and occur with alternatively form by the link units that used alefinically unsaturated compounds derives from, this polymkeric substance can by with monomer be R by dihalide palladium and general formula 1R 2P-R-PR 3R 4The complex compound that forms of phosphorous bidentate ligand prepare for the catalyst composition on basis contacts, in general formula, R 1, R 2, R 3, R 4Be identical alkyl or the different alkyl that has polar group to replace with the property selected, R is for containing the divalent organic bridge base of two carbon atoms at least in its bridge.
Applicant finds in the research to this class catalyst composition, with alkyl replace in dihalide palladium/phosphorous bidentate ligand complex compound one with palladium mutually behind the halogen atom of binding the activity of catalyzed polymerization obtain raising greatly.The applicant also to above-mentioned with alkyl replace one with palladium mutually the substitution reaction of the halogen atom of binding study.Result of study is disappointing when just beginning.Attempt by with containing the complex compound and the alkyl magnesium halogen of dihalide palladium, hydrocarbyl lithium compound or dialkyl zinc compound react all effort that realize needed single substitution reaction, it seems the result that all can cause two halogen atoms all to be replaced by alkyl.Further research makes the investigator find a kind of method, this method make with alkyl might only replace in above-mentioned dihalide palladium/phosphorous bidentate ligand complex compound one with the palladium halogen atom of binding mutually.Further discover this method not only can be used for replacing in dihalide palladium/phosphorous bidentate ligand complex compound (this phosphorous bidentate ligand meets the general formula that the front is given) one with the palladium halogen atom of binding mutually, be configured as M-R but also can be used to more at large contain 5Dihalide palladium/bidentate ligand complex compound, the wherein R of the bidentate ligand of-M 5Represent one one-tenth abutment group, M partly is selected from phosphorus, sulphur, nitrogen, arsenic, antimony and C=C.When this class bidentate ligand and the complexing of dihalide palladium, Cheng Jian between the two M groups in palladium atom and the bidentate ligand.The method that being used for of being found replaces a halogen atom in dihalide palladium/phosphorous bidentate ligand complex compound comprise with this complex compound with contain four with the tin tin compound reaction of binding group mutually, three in four groups is identical or different alkyl, the 4th remaining group both can be alkyl, also can be hydrogen or halogen atom.This method is used for dihalide palladium/phosphorous bidentate ligand complex compound, and wherein phosphorous bidentate ligand has following general formula R 1R 2P-R-PR 3R 4, reaction obtains being fit to hydrocarbyl palladium halide/phosphorous bidentate ligand complex compound of using in the catalyst composition of the present invention.When this method was used to contain the dihalide palladium of other bidentate ligand/bidentate ligand complex compound, reaction obtained hydrocarbyl palladium halide/bidentate ligand complex compound, is R with this complex compound and general formula 1R 2P-R-PR 3R 4Compound reaction just can make needed hydrocarbyl palladium halide/phosphorous bidentate ligand complex compound simply.
By hydrocarbyl palladium halide and general formula is R 1R 2P-R-PR 3R 4The catalyst composition formed of the complex compound of phosphorous bidentate ligand be novel catalyzer.The method for preparing hydrocarbyl palladium halide/bidentate ligand complex compound also is new, and this method is with the dihalide palladium and contains M-R 5The complex compound of the bidentate ligand of-M configuration and the reaction of previously described tin compound, subsequently, if contained bidentate ligand does not meet general formula R in the complex compound of gained 1R 2P-R-PR 3R 4Requirement, be R with general formula more then with this complex compound 1R 2P-R-PR 3R 4The reaction of phosphorous bidentate ligand be converted into the complex compound that suits the requirements.
Therefore, present patent application relates to hydrocarbyl palladium halide and the logical R that becomes 1R 2P-R-PR 3R 4The complex compound of phosphorous bidentate ligand be the novel catalyst composition on basis.Secondly, present patent application also relates to this catalyst composition in the application that is prepared by carbon monoxide and one or more alefinically unsaturated compounds in the polymkeric substance, also relates to the polymkeric substance of preparation thus and the finished product that contain this polymkeric substance to small part.At last, present patent application relates to the preparation hydrocarbyl palladium halide and is configured as M-R 5The method of the bidentate ligand complex compound of-M, this method be with the complex compound of dihalide palladium and corresponding bidentate ligand with contain four with tin mutually the tin compound of binding group react, three in these four groups is identical or different alkyl, and the 4th group both can be alkyl, also can be hydrogen or halogen atom; Subsequently, if contained bidentate ligand does not meet general formula R in the resulting complex compound 1R 2P-R-PR 3R 4Requirement, be R with general formula more then with this complex compound 1R 2P-R-PR 3R 4The reaction of phosphorous bidentate ligand be converted into satisfactory complex compound.
At general formula is R 1R 2P-R-PR 3R 4Phosphorous bidentate ligand in, R 1, R 2, R 3, R 4Be that identical group is good.That be fit to very that the present invention requires then is R wherein 1, R 2, R 3And R 4For not being substituted the phosphorous bidentate ligand of phenyl; And R 1, R 2, R 3, R 4Be phenyl ring that contains one or more alkoxyl groups and this phosphorous bidentate ligand in ortho position that wherein has at least an alkoxyl group to be in the phosphorus atom that links with phenyl ring.Abutment R in the phosphorous bidentate ligand preferably contains the abutment of three carbon atoms in bridge.The example of suitable abutment R has-CH 2CH 2CH 2-,-CH 2-C(CH 3) 2-CH 2-and-CH 2-Si(CH 3) 2-CH 2-.Hydrocarbyl palladium halide in complex compound is the methyl Palladous chloride preferably.
As previously mentioned, the complex compound of dihalide palladium and corresponding bidentate ligand is made hydrocarbyl palladium halide and contains with the reaction of foregoing tin compound be configured as M-R 5The complex compound of the bidentate ligand of-M.If react the bidentate ligand general molecular formula R in the initial complex compound 1R 2P-R-PR 3R 4Requirement, then its reaction product is exactly the complex compound that can be used for catalyst composition of the present invention.If react initial complex compound is the complex compound that contains other bidentate ligand, and then reaction product is exactly a kind of complex compound, is R with it and general formula 1R 2P-R-PR 3R 4Bidentate ligand reaction can make the complex compound that is suitable as catalyst composition of the present invention.Example with other bidentate ligand of bidentate palladium complexing in as the compound of reaction initial feed has: wherein M is that the bidentate ligand of nitrogen-atoms is as 2,2 '-two pyridines and 1,10-phenanthroline; Wherein M is bidentate ligand such as two (diphenylphosphino) methane of phosphorus atom; Wherein M be the bidentate ligand of sulphur atom as 1, two (thiophenyl) propane of 3-; Wherein M be the bidentate ligand of C=C base as 1,5-cyclooctadiene and norbornadiene; Wherein M be the bidentate ligand of arsenic atom as 1, two (phenylbenzene arsyl) propane of 3-.In preparation process, the bidentate palladium in the initial complex compound is palladium chloride preferably.In the method for the invention, for replace with alkyl one with the palladium atom halogen atom of binding mutually, used tin compound, in this tin compound, with tin atom mutually in the group of binding can be hydrogen or halogen atom, for example tri-butyl tin hydride and trimethyltin chloride.Preferably tin compound be wherein four with tin atom mutually the group of binding all be alkyl, especially the tin compound that four groups are all identical is better.The example of the tin compound that is suitable for has tin tetramethide, tin tetraethyl, "four news" (new ideas amyl group tin, tetrabenzyl tin, trimethylphenyl tin and trimethyl benzyl tin.Preferably use for example tin tetramethide of four tin compounds all identical with the group of tin atom phase binding.The polyreaction of use catalyst composition of the present invention preferably adopts carries out monomer and the contacted way of catalyst composition solution that insoluble or insoluble in fact thinner is made into by polymerisate.Very Shi Yi thinner is lower alcohols such as methyl alcohol.If desired, polyreaction also can be carried out under gas phase condition.Utilize catalyst composition of the present invention can be suitably to be the compound formed by carbon and hydrogen fully of a class and except hydrocarbon, also to contain one or more heteroatomic compounds with carbon monoxide polymeric alefinically unsaturated compounds.Catalyst composition of the present invention is preferably used in the multipolymer of preparation carbon monoxide and one or more alefinically unsaturated compounds.The suitable monomeric example of hydro carbons has ethene and other alpha-olefin such as propylene, 1-butylene, 1-hexene and 1-octene.Catalyst composition of the present invention is particularly useful for making the multipolymer of carbon monoxide and ethene and is used to prepare the terpolymer of carbon monoxide and ethene and another kind of alpha-olefin (particularly propylene).The consumption that is used to prepare the required catalyst solution of polymkeric substance can in very large range change.Desire the needed catalyst levels of polymeric alefinically unsaturated compounds to contain 10 for every mole -7-10 -3The mole palladium is more suitable, preferably contains 10 -6-10 -4The mole palladium.
The preparation polymer reaction is preferably in temperature and is lower than 75 ℃, and pressure divides under the 0.2-15 MPa condition and carries out, and is preferably in temperature and is lower than 50 ℃, and pressure is to carry out under the 0.5-10 MPa condition.In desiring the polymeric mixture molar ratio of alefinically unsaturated compounds and carbon monoxide with 10: 1～1: 10 for well, preferably 5: 1～1: 5.
By the following example the present invention is set forth now.
Embodiment 1
Methyl Palladous chloride and 2,2-dimethyl-1, two (the diphenylphosphino)-2-sila propane of 3-etc. the mole complex compound make as follows and separate.Toward the palladium chloride and 2 by 2mmol, 2-dimethyl-1 adds the 4mmol tin tetramethide in the suspension that waits mole complex compound and 10ml methylene dichloride and 10ml methyl alcohol mixed liquor to form of two (the diphenylphosphino)-2-sila propane of 3-.After at room temperature stirring two hours, under reduced pressure the solvent in the reaction mixture is steamed.Remnant is at every turn with 5ml ether washing three times, vacuum-drying at room temperature then.Products therefrom is 1.15 gram methyl Palladous chlorides and 2,2-dimethyl-1, the complex compound such as mole such as grade of two (the diphenylphosphino)-2-sila propane of 3-.
Embodiment 2
Methyl Palladous chloride and 2,2-dimethyl-1, two (diphenylphosphino) propane of 3-etc. the mole complex compound prepare as follows.Past by 2mmol palladium chloride and 2,2-dimethyl-1, adding 4mmol tin tetramethide in the suspension that the mixed solution that waits mole complex compound and 50ml methylene dichloride and 50ml methyl alcohol of two (diphenylphosphino) propane of 3-is formed.Widely different stream under reduced pressure steamed the solvent in the reaction mixture after three hours under argon atmospher.Residue is dissolved in the 5ml methylene dichloride, adds the 25ml ether then.Filter out the gained solids, after the washing of 5ml ether, vacuum-drying at room temperature.Products therefrom is 0.95 gram methyl Palladous chloride and 2,2-dimethyl-1, the complex compound such as mole such as grade of two (diphenylphosphino) propane of 3-.
Embodiment 3
Carbon monoxide/ethylene copolymer prepares as follows.Toward a volume is to add the methyl Palladous chloride and 2 that is made by embodiment 1 by 100ml methyl alcohol and 0.1mmol in the autoclave that stirring of 250ml, 2-dimethyl-1,3-pair of (diphenylphosphino)-2-sila propane etc. the catalyst solution formed of mole complex compound.With all air in the autoclave by vacuumize remove after, the carbon monoxide/ethene gas mixture that injected 1: 1 reaches till the pressure of 4 MPas.After at room temperature stirring 1.5 hours, discharge overbottom pressure and stop polyreaction.The polymer filtration that generates is come out, with vacuum-drying at room temperature after the methanol wash, obtain 1.2 gram multipolymers, polymerization velocity is 75 gram multipolymer/gram palladiums hour.
Embodiment 4
Adopt method substantially the same manner as Example 3 to prepare carbon monoxide/ethylene copolymer, just done following change:
A) with the methyl Palladous chloride and 2 of press embodiment 2 preparation, 2-dimethyl-1, two (diphenylphosphino) propane of 3-etc. mole complex compound as the palladium complex component in the catalyst solution and
B) reaction times is 4 hours rather than 1.5 hours, obtains 1.5 gram multipolymers, and polymerization velocity is 35 gram multipolymer/gram palladiums hour.
Embodiment 5
Basically repeat the experiment of an embodiment 3, the difference just palladium complex in catalyst solution is palladium chloride rather than methyl Palladous chloride.The result is a polymerization reaction take place not.
Embodiment 6
Basically repeat the experiment of embodiment 4, the difference just palladium complex in catalyst solution is palladium chloride rather than methyl Palladous chloride.The result is polymerization reaction take place not.
Embodiment 7
Adopt method substantially the same manner as Example 3 to prepare carbon monoxide/ethylene copolymer, just do the following change:
A). contain 0.1mmol palladium chloride and 1 in the catalyst solution, the complex compound such as mole such as grade of two (diphenylphosphino) propane of 3-is as the palladium complex component.
B). temperature of reaction is 110 ℃ rather than room temperature,
C). the reaction times is 2 hours rather than 1.5 hours.
Obtain 1.5 gram multipolymers.Polymerization velocity is 70 gram multipolymer/gram palladiums hour,
In routine 1-7, routine 1-4 is embodiments of the invention.In embodiment 1 and 2, a chlorine atom in the complex compound of palladium chloride and phosphorous bidentate ligand has passed through with the tin tetramethide reaction and by methyl substituted.In embodiment 3 and 4, the palladium complex that makes is used to prepare carbon monoxide and ethene as catalyzer multipolymer will be reacted thus.In embodiment 5-7, the complex compound that adopts palladium chloride and phosphorous bidentate ligand is as catalyzer, and this does not belong to scope of the present invention, quotes these embodiment in the present patent application and uses as a comparison.After being replaced by alkyl based on a halogen atom in the catalyst composition of the complex compound of palladium chloride and phosphorous bidentate ligand, catalyst activity increases, this point by the result with embodiment 5 and 6 compare with the result of embodiment 3 and 4 respectively (polymerization velocity is increased to 75 and 35 gram multipolymer/gram palladiums hour from 0 respectively) obtain definite confirmation.Result by comparing embodiment 3 and 7 confirms that also above-mentioned catalytic activity increases.In embodiment 3, the catalyst composition that contains methyl Palladous chloride and phosphorous bidentate ligand complex compound by use has at room temperature obtained the polymerization velocity of 75 gram multipolymer/gram palladiums hour.In embodiment 7, adopt under 110 ℃ of temperature, react when containing the palladium chloride complex compound rather than containing the catalyst composition of methyl palladium chloride complex just to reach corresponding polymerization velocity (70 restrain multipolymer/gram palladiums hour).
By means of 13C-NMR analyzes carbon monoxide/ethylene copolymer of knowing by embodiment 3,4 and the preparation of 7 methods and has linear structure, and is to occur with alternatively form by carbon monoxide link units that derives from and the link units that is derived from by ethene wherein.

Claims (5)

1, the method for the polymkeric substance of preparation carbon monoxide and one or more alefinically unsaturated compounds, it is characterized in that monomer contacts with catalyst composition based on the complex compound of alkyl palladium halogen compound and phosphorous bidentate ligand, described alkyl has maximum 5 carbon atoms, the general formula R of phosphorous bidentate ligand 1R 2P-R-PR 3R 4, R in the formula 1, R 2, R 3And R 4Be identical alkyl or the different alkyl that has polar group to replace with the property selected, R is the divalent organic bridge base that contains two carbon atoms in its bridge at least.
2, the described method of claim 1 is characterized in that the R in phosphorous bidentate ligand 1, R 2, R 3And R 4Group or unsubstituted phenyl, or contain the phenyl that one or more alkoxyl groups replace and wherein have at least an alkoxyl group to be in and the phenyl ring ortho position of the phosphorus atom of binding mutually.
3, the described method of claim 1 is characterized in that alkyl halide palladium wherein is the methyl Palladous chloride.
4, each described method of claim 1-3 is characterized in that the solution of monomer and or catalyst composition that essence insoluble thinner be made into insoluble with polymerisate is contacted.
5, each described method of claim 1-3, it is characterized in that polyreaction carries out being lower than under 75 ℃ of temperature and the 0.2-15 MPa pressure, treat that alefinically unsaturated compounds in the polymeric mixture is 10 to the mol ratio of carbon monoxide: 1-1: 10, and every mole treat the polymeric alefinically unsaturated compounds will with the amount of catalyst composition be to make wherein to contain 10 -7-10 -3The mole palladium.
CN90100394A 1989-01-26 1990-01-24 Catalyst Compsns. Expired - Fee Related CN1028108C (en)

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KR100789141B1 (en) * 2006-12-28 2007-12-28 주식회사 효성 Process for producing polyketone
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EP2213644A1 (en) 2009-01-28 2010-08-04 Hexion Specialty Chemicals Research Belgium S.A. Process for the preparation of an allyl alkyl ether by catalyic allylation
EP2213645A1 (en) 2009-01-28 2010-08-04 Hexion Specialty Chemicals Research Belgium S.A. Process for the preparation of an allyl aryl ether by catalytic o-allylation
CN103102373B (en) * 2012-12-27 2015-11-11 中国科学院化学研究所 There is chirality novel divalent palladium title complex bearing counter ion and preparation method thereof

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CN1044469A (en) 1990-08-08
KR900011792A (en) 1990-08-02
EP0380162B1 (en) 1995-04-12
EP0380162A2 (en) 1990-08-01
ATE121108T1 (en) 1995-04-15
BR9000285A (en) 1990-11-27
JPH02233724A (en) 1990-09-17
DE69018488T2 (en) 1995-09-21
AU627830B2 (en) 1992-09-03
EP0380162A3 (en) 1991-08-21
CA2008443A1 (en) 1990-07-26
JP2857195B2 (en) 1999-02-10
US5025091A (en) 1991-06-18
ES2070993T3 (en) 1995-06-16
AU4884890A (en) 1990-08-02
US5145823A (en) 1992-09-08
DE69018488D1 (en) 1995-05-18

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